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United States Patent FLUGRESiZENT AGENTS William Wilson Williams andHarlan Benjamin Freyerninth, Easton, Pa., assignors to General Aniline &Film Corporation, New York, N. Y., a corporation of Delaware No Drawing.Application ()ctober 9, 1951, Serial No. 250,572

4 Claims. (Ci. 260-2411) This invention relates to novel fluorescentagents of the triazinylstilbene series containing a lower aliphaticether group which have been found to be of particular value as opticalbleaching agents especially for incorpora tion in soaps and otherdetergents.

The novel fluorescent agents of the present invention may be representedby the following general formula:

Formula I wherein R represents lower alkyl (e. g. residue of methanol,ethanol, isopropanol, Cellosolve, Carbitol, 2- phenylethanol and thelike), lower alkenyl (e. g. residue of allyl alcohol, methallylalcohol,Z-chloroallyl alcohol and the like) and lower alkynyl (e. g. residue ofpropargyl alcohol). X represents OR or NH2 or the residue of a primaryor secondary amine, for instance, alkylamine or substituted alicylaminesuch as CH3NH--, (CH3)2N-, C2H5NH-, (C2H5)2N-, (CH3)2CHNR,

i2=C4H9NH, sec. C4H9NH-, +C12H25NH HGCH2CH2NH, -NHCH2OH, etc., arylaminosuch as CBH5NH, ClCsH4NH-, CH3CeH4Ni-l CH30C6H4NH, CF3CGH4NH, ClUH'lNH-(naphthylamino), CMHQNI'I- (anthrylamino) HO3SCBH4NH, (CH3)2C6H3NH,etc., heterocyclic such as aminothiazole, aminobenzothiazole,aminotetrazole, etc. alicyclic such as cyclohexylamine,tetrahydronaphthylamine, etc. X may also be a cyclic amine such aspyrimidine, pyrrolidine, piperidine, morpholine and thiornorpholine. Zrepresents the group .COOM or AOzM in which M representshydrogen or acation, usuahy alkali metal .(i. e. sodium or potassium) or ammonium,aLrylol amine, etc., or alkaline earth metal such as barium or calcium.

These novel compounds are readily prepared by condensing a4,4'-diaminostilbene sulfonic or carboxylic acid with cyanuric chloride(or cyanuric bromide, if preferred), two molecular proportions ofcyanuric halide being employed for each molecular proportion of the4,4-diaminostilbene acid.

As the 4,4-diaminostilbene acid employed in this primary condensation,there is preferably used 4,4'-di amino-2,2-stilbene disulfonic acid.This material is commercially valuable and the novel products derivedtherefrom are strong fluorescers. However, other 4,4'-diaminostilbeneacids such as 4,4'-diamino-3,3-stilbene disulfonic acids;4,4'-diamino-2,2', 6,6'-stilbene tetrasultonic acid, may be used, ifdesired, and valuable products may also be obtained by the use of4,4-diamino-stilbene carboxylic acids such as 4,4-diamino-2,2'-stilbenedicarboxylic acid or 4,4'-diamino-3,3'-stilbenedicarboxylic acidalthough in general the derivatives of the diaminostilbenecarboxylicacids fluoresce somewhat weakly than the corresponding derivatives ofthe sulfonic acids.

By the condensation of a 4,4'-diaminostilbene acid with cyanuricchloride there is obtained as a primary condensation product the triazylderivative of the acid. This primary condensation product is thenfurther condensed with two molecular proportions of an aliphatic alcoholsuch as preferably a lower alkanol, such as ethanol, methanol,isopropanol, etc. and two molecular proportions of primary or secondaryamine. The condensation of the triazyl derivative of the diaminostilbeneacid with 'the alcohol and the ammonia or amine may be carried out inany order advantageously. However, the triazyl derivative may becondensed with an aliphatic alcohol whereby there is obtained a novelintermediate product Formula 11 wherein X stands for chlorine or bromineand R and Z are as defined above.

This novel intermediate product is then finally condensed with ammonia,an alcohol or a primary or secondary amine in order to obtain the novelproducts of the present invention.

These condensations may be carried out by procedures commonly employedin the art for efiecting such condensations. In order to illustratefully the preparation of compounds of the present invention thefollowing detailed illustrations of the preparation of the novelintermediate of the present invention and of specific fluorescent agentsembodied therein are given. The parts are by weight.

EXAMPLE 1 Preparation of intermediate Thirty-seven parts of cyanuricchloride are dissolved in parts of acetone and poured into a mixture ofice and water. During the suspension in ice water, the temperature ofthe aqueous suspension should not rise above 5 C. Thirty-seven parts of4,4'-diamino-2,2-stilbenedisulfonic acid are dissolved in parts of waterwith the addition of enough sodium carbonate to give a neutral solution.This solution is added slowly to the cyanuric chloride suspension and atthe same time a solution of sodium carbonate is added in order to keepthe mixture from becoming too acid. The temperature should not riseabove 5 C. during this condensation. The condensation is complete when asample of the reaction mixture which has been acidified and treated withsodium nitrite does not develop color when treated with an alkalinesolution of R salt. When the condensation is complete, the product isfiltered and the wet press cake is stirred at room temperature for 8hours with 475 parts methanol, 8 parts sodium hydroxide.

' 3 4 There is thus obtained the novel intermediate product4,4'-diamino-2,2'-stilbenedisulfonic acid are dissolved in of Formula IIabove wherein X is chlorine and R is methyl. 150 parts of water with theaddition of enough sodium By replacing the methanol with an equivalentamount of carbonate solution to give a neutral solution. Thissoluethanol there may be obtained an ethan-olic solution of tion isadded to the triazine suspension and a solution of novel intermediateproduct of Formula 11 above wherein 5 160 parts anhydrous sodium acetateand 400 parts X is chlorine and R is ethyl. Likewise by replacing thewater are added. The mixture is allowed to warm to room methanol with anequivalent amount of isopropanol there temperature and is stirred for 24hours. When the conmay be obtained a propanolic solution of novelinterdensation is complete, resulting in the formation of the mediate ofFormula II above wherein X is chlorine and novel intermediate product ofFormula I above wherein R is isopropyl. m X is chlorine and R is methyl,there is added 28 parts of I morpholine and the pH is adjusted to 89 bythe addi- EXAMPLE H tion of a solution of sodium carbonate. The mixtureis Alnovel fluorescent agent of the present invention was heated to80-90 C. for 6 hours. After cooling the then produced from themethanolic solution from the mixture is isolated in the usual manner.The product novel intermediate obtained as described in paragraph 1obtained by this procedure isidentical with the material of Example I asfollows: described in Example II.

To the methanolic solution of the intermediate (without isolation orother purification of the product), 'ob- EXAMPLE V tained as describedin Example I first paragraph there The procedure of Example IV isfollowed except 24.6 was added 809 Parts of Water and 28 Parts ofmorphglme' parts 4-anisidine is used in place of 28 parts of morpholine.

The pH is adjusted to 9.5 by the addition of sodium There is obtained ba y this method a product which is carbonate solution and the mixturethen heated to 80 90 C. for four hours and then cooled and the productIdentical to the one descnbed m Example isolated by filtration anddrying at 70-75" C. There EXAMPLE 1 is thus obtained a compoundcorresponding to the 26 formula: Thirty-seven parts of cyanuric chlorideare dissolved CH CH: C O Hz a O\ N\ N O CHzCg o-N NC onzc N C-HN- CH=CHNH-C N v t doaNa SO3Na 0011:; OCH;

By; treating the novel intermediates (obtained as dein 120 parts ofacetone and poured into a mixture of ice scr bed in paragraph of ExampleI) 1n the manner 16' and water. During the suspension in ice water, thetemscribed in the preceding paragraph there are obtained perature of theaqueous suspension should not rise above compounds of similar propertieswhere n the methyl 40 5 C. Thirty-seven parts of4,4'-diamino-2,2'-stilbenedigroup of the compoundnllustrated immediatelyabove is sulfonic acid are dissolved in 150 parts of water with thereplaced by ethyl and isopropyl groups, respectively. addition of enoughsodium carbonate to give a neutral solution. This solution is addedslowly to the cyanuric EXAMPLE H1 chloride suspension and at the sametime a solution of The novel intermediate product obtained as describedsodnfm carbohate 15 added torkeep the mixture' from in paragraph 1 ofExample I is treated (without isolation C(Zmmg The tempatrfimre shouldnot use or purification of the material obtained) by adding thereto 5dul'mg thls @ndematmn' h 15 800 parts of water and 24.6 parts of4-anisidine. The Complete hh a Sample of the reactlon fixture Whlch pHis adjusted to 9 95 by the addition of sodium has been acidified andtreated with sodium nitrite does not bonate Solution and the mixture ishated to C- develop a color when treated with an alkaline solution forfour hours. It is then cooled, the product recovered V of R The Solidmaterial is removed y filtration and by filtration and dried at from -75C. There is then the wet filter cake is slurried with a mixture of 16parts obtained a compound corresponding to the formulaof sodiumhydroxide and 675 parts of methanol which orn0ONn 0on3 I No-HNQon=onQNH-o N o=N N=o l OzNa t O Na GHaO CH:

EXAMPLE IV previously has been cooled to'0 C. The mixture is stirred36.2 parts of 2-methoxyl-4,6-dichloro-'1,3,5triazine (pre at 0 for tenmmutes at room tempera/Elm fol-filmy pared by the reaction of aqueousmethanol on cyan minutes and at reflux temperature for thirty minutes.chloride in the presence of sodium bicarbonate) .is dis- The slurry isallowed to Cool to m tempefahll'fi and is solved in parts acetone andthis solution is poured isolated in the 1151131 The Product correspondsinto a mixture of ice and water. Thirty-seven parts of to the followingstructure: a

EXAMPLE VII 37 parts of cyanuric chloride are dissolved in 120 parts ofacetone and poured into a mixture of ice and water. During thesuspension in the ice water the temperature of the aqueous suspensionshould not rise above 5 C. 37 parts of4,4-diamino-2,2-stilbenedisulfonic acid are dissolved in 150 parts ofwater with the addition of enough sodium carbonate to give a neutralsolution. This solution is then added slowly to the cyanuric chloridesuspension in ice water and at the same time a solution of sodiumcarbonate is slowly added in order to keep the mixture from becoming tooacid (pH of 3 to 3.5). During this addition and consequent condensationthe temperature should not rise above 5 C. The condensation of thecyanuric chloride with the diaminostilbene disulfonic acid is completewhen a sample of the reaction mixture which has been acidified andtreated with sodium nitrite does not develop color when treated with analkaline solution of R salt.

When this condensation is complete 17.4 parts of morpholine is added tothe thus obtained product and immediately afterwards a solution of 160parts of anhydrous sodium acetate in 400 parts of water is added. Thethus obtained mixture is allowed to warm to room temperature and may beheated to 35 to 40 C. if necessary to complete the condensation. Theproduct is filtered and the wet press cake is stirred at roomtemperature for 8 hours with 475 parts of methanol and 16 parts ofsodium hydroxide. The mixture is refluxed for 3 hours and is thencooled, filtered and the product dried at 70-75 C. There is thusobtained a compound identical to that described in Example ll.

EXAMPLE VIII The procedure of Example V11 is followed except that 24.6g. of 4-anisidine are used in place of 17.4 parts morpholine. There isobtained a compound identical to that described in Example HI. v

The foregoing materials were tested by incorporating a small amountthereof in soaps and synthetic detergents (i. e., about 0.1 per cent byweight, 0.025 per cent and 0.5 per cent by weight of the fluorescentagents) in a commercial sodium soap of fatty acids (Lux Flakes) and in asynthetic detergent comprising essentially a mixture of sodium alkylarylsulfonate and sodium phosphates (Tide) and the thus obtained detergent.mixtures employed to wash cellulosic (cotton, rayon), wool and nylonfabrics.

, White materials thus washed were extraordinarily whiter in appearanceand colored materials brighter than similar materials which were washedusing ordinary soaps or detergents which contained no fluorescentagents. The above materials were also incorporated in discharge pastesand applied to fabrics in the usual manner. Whites thus treated wereunusually whiter than those treated using similar discharge pastescontaining no fluorescent agents. The novel agents of this inventionwere applied to cellulosic, wool and nylon fabrics from weakly alkalinebaths whereby the white appearance of the fabric was much improved.

It will be apparent that in the foregoing examples the novel products ofthe present invention were obtained in the form of their sodium salts.However, the potassium salts have substantially similar properties andit will be apparent that the potassium salts will be obtained by usingpotassium carbonate and acetate in place of sodium carbonate and acetateas the alkaline agents for the condensations in the synthesis of thesematerials. The free acids may be obtained by acidification of the sodiumor potassium salt While other salts such as the ammonium or alkylolamine salts may be obtained by neutralization of the free acids. Wherespirit soluble products are desired, for instance, in brightening oflacquers etc. the higher alkyl or cycloalkylamine salts of the freeacids such as the cyclohexylamine salts of the free acids may beproduced by methods known in the art. The alkaline earth metal saltssuch as the barium and calcium salts which may be obtained from the freeacid or by double decomposition of the sodium or potassium salts havebeen foundto be useful for the brightening of photographic prints, etc.

In addition to the compounds described specifically above, a widevariety of valuable fluorescent agents of Formula I above may beobtained by replacing the morpholine or 4-anisidine used in the exampleswith other amines. We particularly prefer the compounds obtained byemploying as the amine, diethanol amine or alkyl and alkoxy substitutedanilines such as 2,4-dimethoxy aniline, 3,5-dimethoxy aniline, 2-methoxytoluidine, ortho and meta anisidines, xylidine and the like.

As valuable amines which may be employed to produce valuable fluorescentagents of Formula I above in which the group X will correspond to theamino radical of the particular amine employed may be mentioned pritaryalkylamines such as methyl-, methylol, ethyl-, ethylol, propyl-,isopropyl-, n.-sec.- or -tert.-, butyl-, dodecyl-, or stearyl-aminoetc.; primary arylamines such as chloro anilines, toluidines,anisidines, xylidines, naphthylamines,

anthrylamine, sulfanilic acid, 3-amino phenol etc., also heterocyclicamines such as Z-aminothiazole, Z-aminobenzothiazole, 2-amino pyrimidineetc., also cycloalkylamines such as cyclohexyl amine, tetrahydronaphthylamine, etc., also alkarylamines such as benzylamine etc. As example ofsecondary amines which may be used may be mentioned the secondary aminescorresponding to any of the above primary amines in which an aminohydrogen has been replaced by an alkyl, aryl, or heterocyclic group, forinstance dialkylamines such as dimethyl-, diethyl, methyl-ethyl-,dibutyl-, diamyl-, methyl-butyl-, methylcyclohexylamines, also N-alkyl,aryl amines such as N-methyl-, N-ethyl-, or N-butylanilines,-anisidines, -naphthylamines, -aminothiazoles, -aminopyridines etc.,also such heterocyclic secondary amines as carbazole, thiomorpholino,pyrrole, pyrrolidino, indole, etc.

The novel fluorescent agents of the present invention fluoresce underultra-violet light with a bluish fluorescence, and since they aresubstantive to cellulosic materials, are particularly valuable forincorporation into soaps and synthetic detergents such as alkyl arylsulfonates, higher fatty acid methyl taurides, non-ionic detergents suchas the polyglycol ethers of alkyl phenols or of partial higher fattyacid esters of mannitol or sorbitol. The fabrics Washed withformulations of detergents containing these fluorescent agents appearmuch whiter in the case of whites and much brighter in the case ofcolors than fabrics which are washed with ordinary soaps or detergents.These fluorescent agents may also be applied to fabrics by separatetreating baths and similar methods and procedures well known in the art.They are also useful when incorporated into paper or other wrappingmaterials, particularly cellulosic wrapping material to improve thewhiteness of such material, as well as to protect the contents from theaction of ultra-violet light. They may also be incorporated in dischargepastes whereby the whites obtained upon discharge are decidedly whiterthan those discharges made in the absence of such materials. They mayalso be used to bleach fabrics and in such cases the amount of bleachnecessary is materially reduced and one or more steps of the normalbleaching operations may be eliminated.

We claim:

1. Fluorescent agents selected from the group consisting of compounds ofthe formula:

C=N J wherein R represents lower alkyl and X represents a member of thegroup consisting of morpholino, anisidino and methoxy, and the salts ofsaid compounds.

SOsH

2. Fluorescent agents which in the form of the free acid have theformula r 3. Fluorescent agents which in the form of the free acid havethe formula 4. Fluorescent agents which in the form of the free acidhave the formula N CHaO(iJ ONH CH=CH NHO/ 0-003; N N N y 30311 0:11 c 0(50m (50H: i

References Cited in the file of this patent UNITED STATES PATENTS OTHERREFERENCES Serial N0. 381,856, Wendt (A. P. 0; published May 11, 1943. VV

1. FLUORESCENT AGENTS SELECTED FROM THE GROUP CONSISTING OF COMPOUNDS OFTHE FORMULA: